JP4999702B2 - Polyester clay nanocomposites for barrier applications - Google Patents

Description

  The present invention is a method of reducing gas permeability through polyester containers and films by incorporating an effective amount of exfoliated sepiolite-type clay into the polymer from which the container or film is formed.

  A nanocomposite is a polymer reinforced with nanometer-sized particles, ie, particles with dimensions of about 1 to several hundred nanometers.

  Polymer layered silicate nanocomposites incorporate layered clay mineral fillers into the polymer matrix. Layered silicates are made up of hundreds of thin platelets that are stacked into regular envelopes known as tactoids. Each of these platelets is characterized by a large aspect ratio (diameter / thickness of about 100 to 1000). Thus, when the clay is uniformly dispersed and peeled as individual platelets throughout the polymer matrix, the strength, bending and Young's modulus are greatly increased, and due to the large surface area contact between the polymer and filler, Heat deflection temperature is observed with a very low filler loading (<10 wt%). Furthermore, the barrier properties are greatly improved. The reason is that the large surface area of the platelets greatly increases the path twist that must be followed when the diffusing species permeate the polymer material.

  Clay minerals and their industrial uses are described in H. M.M. Considered by Murray. Two types of clay minerals, kaolin and smectite, are commonly used in nanocomposites. Kaolin molecules are arranged in two sheets or plates, one of silica and one of alumina. The most widely used smectites are sodium montmorillonite and calcium montmorillonite. Smectite is disposed on two silica sheets and one alumina sheet. The molecules of the montmorillonite clay mineral are weaker than the kaolin group and further apart.

  Since the early development of nylon-based materials by Usuki et al. In 1993, there has been increasing interest in nanocomposites (2). However, few attempts have been made to produce nanocomposites in thermoplastic polyester matrices. For example, it is desirable to disperse and peel clay in polyester to improve barrier properties in packaging applications. Most of the polyester efforts focused on developing polyesters with excellent barrier properties. These efforts have focused on the use of smectite with quaternary ammonium cations including an organic tail. This approach has the disadvantage that although the compounding methodology can be modified, the release agent is not stable at the compounding temperature. In addition, this route generally results only in the formation of tactoids or tactoid aggregates in the polymer matrix.

  Another route for making nanocomposites is exfoliation by polymerization. This approach generally involves dispersing nanofibers, usually smectites such as montmorillonite, in one or more monomers, followed by forming a polymer around the dispersion. One of the points at which this process successfully exfoliates the clay involves selecting an appropriate intercalating agent. The interaction between the intercalator and the monomer must be strong enough to allow the monomer to advance into the clay path. This process therefore requires the use of an intercalating agent, thus causing the same thermal stability problem described above.

  The current literature teaches against the use of an in situ polymerization approach for the preparation of clay nanocomposites. For example, Matayabas et al. Found that polymers prepared with organically modified clays did not show an increase in clay bottom spacing after polymerization, and no new bottom spacing occurred during polymerization. After transesterification, individual platelets were not identified. The formation of individual platelets occurred during the condensation polymerization step of the polymerization process (Non-Patent Document 3).

  A third route used in preparing polyester-based nanocomposites is to use other polymers such as poly (vinyl pyrrolidone) to facilitate exfoliation of the clay into the polymer matrix. Nanocor (R) (Nanocor (R) is a wholly owned subsidiary of AMCOL International Corporation, Arlington, Illinois) and Eastman The Chemical Company (Eastman Chemical Company, Kingsport, Tennessee) has both used this to prepare polyester-based nanocomposites for applications that require materials with superior barrier and mechanical properties. Approaches are utilized (e.g., U.S. Pat. No. 6,057,049, Nanocor (R) and (U.S. Pat. However, this approach typically uses a solvent-based process in which the clay and polymer interact to increase the basal spacing of the clay under a vacuum. If removed later, an inserted smectic clay system is obtained, the material is melt compounded with the desired polymer matrix (generally PET), extruded and pelletized. For example, polymers and clays represent a small weight percent of the intercalating solution, for example, Trexler Jr., JW Piner, RL Turner. (Turner) S.R. and Barbie B. (Patent Document 3) In addition, introduction of a polymer (e.g., poly (vinyl pyrrolidone)) at the interface between the polyester and the clay filler can be accomplished using a polyester matrix and nanoclay filler particles. Change the interaction.

  For the reasons mentioned above, foods such as poly (ethylene terephthalate) (PET) thermoplastic polyester polymers used to produce injection stretch blow molded bottles for packaging water, carbonated soft drinks and beer, among others, and In order to improve the gas barrier performance of molded polyester articles, such as those used to contain beverages, there is a need for an improved process of dispersing and exfoliating filler material in a polymer matrix.

US Pat. No. 5,698,624 International Publication No. 99/03914 Pamphlet International Publication No. 99/03914 Pamphlet Applied Clay Science 17 (2000) 207-221 Usuki A. Et al., Journal of Materials Research, 1993, 8 (5): p. 1179-1184 J. et al. C. Matayabas Jr. “Nanocomposite Technology for Enhancing The Gas Barrier,”, Polymer Clay Nanocomposites (Polymer Clay Nanocomposites), T. J. Pinnav. (Beall), Wiley: New York (2000) 218-222

It is an object of the present invention to provide a method for reducing the gas permeability of molded polyester articles selected from containers, sheets and films. This method
a. Sepiolite-type clay
(I) at least one diacid or diester and at least one diol,
(Ii) at least one polymerizable polyester monomer;
A polyester nanocomposite was prepared by mixing with (iii) at least one linear polyester oligomer, and (iv) at least one polyester precursor selected from the group of at least one macrocyclic polyester oligomer. After, polymerizing at least one polyester precursor, with or without solvent,
b. Forming a molded polymer article comprising the polyester nanocomposite thus produced.

  The nanocomposite contains an effective amount of exfoliated sepiolite-type clay. As used herein, “effective amount” means that the exfoliated sepiolite-type clay is present sufficiently to detectably reduce the permeability of the article to the permeating material (eg, oxygen). . This is 0.1% to 20% by weight of the polyester nanocomposite.

  Polyester articles containing exfoliated sepiolite-type clay, particularly extruded films or injection stretch blow molded polyester (eg, PET) bottles, to corresponding polyester articles containing non-exfoliated sepiolite-type clay In comparison, when measured according to ASTM D3985, the oxygen and carbon dioxide permeability values and when measured according to ASTM D6701, the water vapor permeability values are reduced.

  A number of terms are used in the present disclosure.

  As used herein, the term “nanocomposite” or “polymeric nanocomposite” includes particles (“nanoparticles”) dispersed throughout a polymeric material having at least one dimension in the range of 0.1-100 nm. Means a polymer material. The polymer material in which the nanoparticles are dispersed is often referred to as a “polymer matrix”. The term “polyester composite” refers to a nanocomposite in which the polymeric material comprises at least one polyester.

  As used herein, “sepiolite-type clay” refers to both sepiolite and attapulgite (palygorskite) clay.

  The term “peel” literally refers to dropping flakes, flakes or debris, or spreading or stretching by opening or as if opening leaves. In the case of smectic clays, “peeling” refers to the separation of the platelets from the smectic clay and the dispersion of these platelets throughout the polymer matrix. As used herein, for a sepiolite-type clay that is fibrous in nature, “exfoliated” or “exfoliated” refers to the separation of fiber bundles or aggregates into nanometer diameter fibers, followed by the entire polymer matrix Means to be distributed.

  As used herein, “effective amount” means that the barrier enhancing additive is present sufficiently to detectably reduce the permeability of the article to the permeating material (eg, oxygen). This is 0.1% to 20% by weight of the polyester nanocomposite.

As used herein, an “alkylene group” means —C _n H _2n — (where n ≧ 1).

As used herein, “cycloalkylene group” means a cyclic alkylene group, —C _n H _2n-x — (wherein x represents the number of H substituted by cyclization).

As used herein, a “mono- or polyoxyalkylene group” refers to [—— (CH ₂ ) _y —O——] _n — (CH ₂ ) _y —— where y is an integer greater than 1. , N is an integer greater than 0).

  As used herein, “alicyclic group” means a non-aromatic hydrocarbon group containing a cyclic structure therein.

  As used herein, “divalent aromatic group” means an aromatic group having bonds to other parts of the macrocyclic molecule. For example, a divalent aromatic group may include a meta- or para-linked monocyclic aromatic group.

  As used herein, “polyester” means a condensation polymer in which 50 percent or more of the groups connecting the repeating units are ester groups. Thus, the polyester may contain polyester, poly (ester-amide) and poly (ester-imide) as long as more than half of the linking groups are ester groups. Preferably at least 70% of the linking groups are esters, more preferably at least 90% of the linking groups are esters, particularly preferably substantially all of the linking groups are esters. The ratio of the ester linking group can be estimated by a first order approximation based on the molar ratio of the monomers used to prepare the polyester.

  As used herein, “PET” means that at least 80, more preferably at least 90 mole percent of the diol repeat units are from ethylene glycol, and preferably at least 80, more preferably at least 90 mole percent of the dicarboxylic acid repeat units are terephthalic. It means a polyester that is from an acid.

  As used herein, “polyester precursor” means a material that can be polymerized into polyesters, polymerizable polyester monomers and polyester oligomers, such as diacid (or diester) / diol mixtures.

  As used herein, “polymerizable polyester monomer” means a monomeric compound that polymerizes with itself or other monomers (also present). Examples of such compounds include hydroxybenzoic acid and hydroxyacids such as hydroxynaphthoic acid and bis (2-hydroxyethyl) terephthalate.

  As used herein, “oligomer” means a molecule that contains two or more identifiable structural repeat units of the same or different formula.

  As used herein, “linear polyester oligomer” means an oligomeric material excluding macrocyclic polyester oligomers (see below) that can be polymerized to high molecular weight polyesters by themselves or in the presence of monomers. Examples of the linear polyester oligomer include linear polyester oligomers and polymerizable polyester monomer oligomers. For example, when carried out to remove methyl ester or carboxyl groups, the reaction of dimethyl terephthalate or terephthalic acid with ethylene glycol usually results in oligomers of bis (2-hydroxyethyl) terephthalate, mono (2-hydroxyethyl) terephthalate A mixture of various oligomers, such as oligomers (containing carboxyl groups) and further extendable polyester oligomers, with bis (2-hydroxyethyl) terephthalate. In the practice of the present invention, preferably the average degree of polymerization (average number of monomer units) of such oligomers is about 20 or less, more preferably about 10 or less.

  As used herein, a “macrocycle” molecule refers to a cyclic molecule having at least one ring in its molecular structure containing 8 or more atoms covalently bonded to form a ring.

  As used herein, “macrocyclic polyester oligomer” means a macrocyclic oligomer containing two or more distinguishable structural repeat units of the same or different formula. Macrocyclic polyester oligomers generally refer to multiple molecules of one particular formula having different ring sizes. However, macrocyclic polyester oligomers may also contain multiple molecules of different formulas having different numbers of identical or different structural repeat units. The macrocyclic polyester oligomer may be a co-oligoester or multi-oligoester, i.e. a polyester oligomer having two or more different structural repeat units having one ester functional group in one cyclic molecule. .

  Where numerical ranges are listed herein, unless otherwise stated, ranges are intended to include endpoints and integers and fractions within the range. The scope of the invention is not considered to be limited to the specific values recited when defining a range.

It is an object of the present invention to provide a method for reducing the gas permeability of molded polyester articles generally selected from containers, sheets and films. This method
a. Sepiolite-type clay
(I) at least one diacid or diester and at least one diol,
(Ii) at least one polymerizable polyester monomer;
A polyester nanocomposite was prepared by mixing with (iii) at least one linear polyester oligomer, and (iv) at least one polyester precursor selected from the group of at least one macrocyclic polyester oligomer. After, polymerizing at least one polyester precursor, with or without solvent,
b. Forming a molded polymer article comprising the polyester nanocomposite thus produced.

Preparation of Polyester Nanocomposite The nanocomposite contains an effective amount of exfoliated sepiolite, exfoliated attapulgite or a mixture of exfoliated sepiolite and exfoliated attapulgite. As used herein, “effective amount” means that the barrier enhancing additive is present sufficiently to detectably reduce the permeability of the article to the permeating material (eg, oxygen). This is 0.1% to 20% by weight of the polyester nanocomposite.

Sepiolite and attapulgite Clay minerals and their industrial uses are described in Applied Clay Science 17 (2000) 207-221 in H.C. H. Considered by Murray. Two types of clay minerals, kaolin and smectite, are commonly used in nanocomposites. Kaolin molecules are arranged in two sheets or plates, one of silica and one of alumina. The most widely used smectites are sodium montmorillonite and calcium montmorillonite. Smectite is disposed on two silica sheets and one alumina sheet. The molecules of the montmorillonite clay mineral are weaker than the kaolin group and further apart.

Sepiolite _{[Mg 4 Si 6 O 15 (} OH) 2 · 6 (H 2 O)] is a hydrated magnesium silicate filler that exhibits a high aspect ratio due to its fibrous structure. Of the silicates, sepiolite is composed of long lath crystallites whose silica chains extend parallel to the fiber axis. It has been found that the material consists of two forms, the α and β forms. The α form is known to be a long bundle of fibers, and the β form exists as amorphous aggregates.

  Attapulgite (also known as palygorskite) is structurally and chemically almost identical to sepiolite, except that attapulgite has slightly smaller unit cells. As used herein, the term “sepiolite type clay” includes attapulgite as well as sepiolite itself.

  Sepiolite-type clay made of two sheets of tetrahedral silica units bonded to a central sheet of octahedral units each containing magnesium ions is a layered fibrous material (eg, L. Bokobza et al. (See, Polymer International 53, 1060-1065 (2004), FIGS. 1 and 2). The fibers stick together to form a fiber bundle, which in turn can form an aggregate. These agglomerates can be broken up by industrial processes such as micronization or chemical modification (see, for example, EP 170,299, Tolsa SA).

  The amount of sepiolite-type clay used in the present invention is about 0.1 to about 20% by weight based on the final composite composition. The particular amount selected depends on the intended use of the nanocomposite, as is well known in the industry.

  Sepiolite-type clays are of high purity (“rheological grade”) uncoated form (eg, PANGEL® S9 sepiolite clay from Tolsa Group, Madrid, Spain, Madrid), More generally, it is treated with an organic material to make it more “organic compatible”, ie, compatible with low to medium polar systems (eg, Tolsa Group pangels ( (PANGEL) (registered trademark) B20 sepiolite clay). An example of such a coating of sepiolite-type clay is a quaternary ammonium salt, such as dimethyl benzyl alkyl ammonium chloride, as disclosed in European Patent Application No. 221,225.

  When smectic clays (eg, montmorillonite) are uniformly dispersed throughout the polymer matrix and exfoliate as individual platelets, the barrier properties are greatly improved because of the large surface area of the platelets, the diffusion species being the polymer material This is to greatly increase the twist of the path that must be followed when penetrating through. However, sepiolite-type clay peels into long lath crystallites. Thus, it is very surprising that exfoliated sepiolite type clay is effective in increasing the barrier properties of the polymer matrix in which it is incorporated.

Polyester The polyester used may be any polyester with the required melting point. The melting point of the polyester is preferably about 150 ° C. or higher, more preferably about 200 ° C. or higher. Polyesters (most or all have ester linking groups) are usually derived from one or more dicarboxylic acids and one or more diols. They can also be produced from polymerizable polyester monomers or macrocyclic polyester oligomers.

  The most suitable polyester for use in the practice of this invention comprises isotropic thermoplastic polyester homopolymers and copolymers (both block and random).

Formation of polyesters from diols and hydrocarbyl diacids or esters of such diacids is J. et al. East, M.C. Golden and S.H. Mahhija, Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley & Sons, J. et al. I. Editor-in-chief of Kroschwitz It is well known in the industry as described in Howe-Grant, 4th edition (1996), volume 19, 609-653. In the first stage, esterification or transesterification occurs between the diacid or its dialkyl (typically dimethyl) ester and the diol, in addition to the generation and removal of water or alcohol (typically methanol). Bis (hydroxyalkyl) esters and some oligomers are thus obtained. Since esterification or transesterification is inherently a slow reaction, a catalyst is generally used. Examples of useful esterification or transesterification catalysts are calcium acetate, zinc and manganese, tin compounds and titanium alkoxides. In the second stage, polycondensation, bis (hydroxyalkyl) esters and oligomers continue to transesterify, eliminating diol removed under high vacuum and increasing molecular weight. Useful polycondensation catalysts are exemplified by tin and titanium compounds, antimony and germanium compounds, particularly antimony oxide (Sb ₂ O ₃ ) in the case of PET.

  Suitable diacids (and their corresponding esters) are terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid fumaric acid, Selected from the group consisting of maleic acid and derivatives thereof such as, for example, dimethyl, diethyl or dipropyl esters.

  Representative examples of glycols that can be used as the diol component include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 2,2-diethyl-1,3-propanediol, and 2,2-dimethyl- 1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4- Cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, isosorbide Naphthalene glycols, diethylene glycol, triethylene glycol, resorcinol, hydroquinone, and long chain diols and polyols such as polytetramethylene ether glycol is the reaction product of an alkylene oxide with a diol or polyol.

In one preferred type of polyester, the dicarboxylic acid is one or more of terephthalic acid, comprises isophthalic acid and 2,6-naphthalene dicarboxylic acid, the diol component is one or more HO (CH _{2) n} OH (I), 1,4- _{cyclohexanedimethanol, HO (CH 2 CH 2 O} ) m CH 2 CH 2 OH (II) and _{HO (CH 2 CH 2 CH 2} CH 2 O) z CH 2 CH 2 CH ₂ CH ₂ OH (III) (wherein n is an integer from 2 to 10, m is 1 to 4 on average, and z is about 7 to about 40 on average). Note that (II) and (III) are mixtures of compounds that are not whole numbers because m and z are different, and therefore m and z are averages. In preferred polyesters, n is 2, 3 or 4 and / or m is 1.

  Polyesters can also be produced directly from polymerizable polyester monomers. Representative examples of polymerizable polyester monomers suitable for use in the present invention include hydroxy acids such as hydroxybenzoic acid, hydroxynaphthoic acid and lactic acid, bis (2-hydroxyethyl) terephthalate, bis (4-hydroxybutyl) terephthalate. Bis (2-hydroxyethyl) naphthalenedioate, bis (2-hydroxyethyl) isophthalate, bis [2- (2-hydroxyethoxy) ethyl] terephthalate, bis [2- (2-hydroxyethoxy) ethyl] isophthalate Bis [(4-hydroxymethylcyclohexyl) methyl] terephthalate and bis [(4-hydroxymethylcyclohexyl) methyl] isophthalate, mono (2-hydroxyethyl) terephthalate, bis (2-hydroxyethyl) sulfoiso Tallates and lactide, and the like.

  Polyesters can also be produced directly from macrocyclic polyester oligomers. Macrocyclic polyester oligomers that may be used in the present invention include, but are not limited to, macrocyclic poly (alkylene dicarboxylate) oligomers having structural repeat units of the following formula:

  Where A is an alkylene, cycloalkylene or mono- or polyoxyalkylene group containing at least two carbon atoms and B is a divalent aromatic or alicyclic group. They are disclosed in US Pat. Nos. 5,039,783, 5,231,161, 5,407,984, 5,668,186, and US provisional. Patent application 60/626187, PCT patent application WO2003309491 and WO2002068496 and A. Lavallette et al., Biomacromolecules, Volume 3, p. It may be prepared in various ways as described in 225-228 (2002). Macrocyclic polyester oligomers can also be obtained by extrusion from low molecular weight linear polyesters.

  Preferred macrocyclic polyester oligomers are 1,4-butylene terephthalate (CBT), 1,3-propylene terephthalate (CPT), 1,4-cyclohexylene dimethylene terephthalate (CCT), ethylene terephthalate (CET), 1,2 -A macrocyclic polyester oligomer of ethylene 2,6-naphthalenedicarboxylate (CEN), a cyclic ester dimer of terephthalic acid and diethylene glycol (CPEOT), and a large comprising two or more of the above structured repeat units Cyclic co-oligoester.

  The polyester may or may not be branched, and may be a homopolymer or copolymer, or a polymer blend comprising at least one such homopolymer or copolymer.

  Specific preferred polyesters include poly (ethylene terephthalate) (PET), poly (1,3-propylene terephthalate) (PPT), poly (1,4-butylene terephthalate) (PBT), poly (1,4-butylene terephthalate). ) And a poly (tetramethylene ether) glycol block thermoplastic elastomeric polyester (EI du Pont de Nemours and Co. Inc., USA) 1998, available as HYTREL® from Wilmington, Del., Poly (1,4-cyclohexyldimethylene terephthalate) (PCT) and Polylactic acid (PLA) and the like. PET is particularly preferred.

  Of particular note are “modified polyesters” defined as modified with up to 10% by weight of comonomer. Unless otherwise noted, the term polyester polymer (or oligomer) refers to modified and unmodified polyester polymers (or oligomers). Similarly, when referring to a specific polyester, for example, poly (ethylene terephthalate) (PET) means unmodified or modified PET. Examples of the comonomer include diethylene glycol (DEG), triethylene glycol, 1,4-cyclohexanedimethanol, isosorbide, isophthalic acid (IPA), 2,6-naphthalenedicarboxylic acid, adipic acid, and mixtures thereof. In general, the preferred comonomer of PET contains 0-5 wt% IPA and 0-3 wt% DEG.

  In a particularly preferred embodiment of the present invention, the polyester base polymer is polyethylene terephthalate (PET) comprising a PET polymer that has been modified with about 2 mol% to about 5 mol% of isophthalate units. Such modified PET is known as a “bottle grade” resin and is a MELINAR® laser (LASER) from ADVANSA, a wholly owned company of Haci Omer Sabanci AS, Turkey. ) + (Registered trademark) polyethylene terephthalate brand resin.

Process Conditions The process conditions for producing the nanocomposite material are the same as those known in the industry for producing polyesters in a melt or solution process. Sepiolite clay mineral can be added by any means at any convenient manufacturing stage before the degree of polyester polymerization is about 20. For example, it can be added with the monomer first, during monomer esterification or transesterification, at the end of monomer esterification or transesterification, or early in the polycondensation process.

  Various catalysts can be used if DEG production needs to be controlled during the reaction. The lithium acetate buffer described in US Pat. No. 3,749,697, and described in JP 83-62626, RO 88-135207, and JP 2001-105902 And the use of various sodium acetate and potassium buffers. In general, 100-600 ppm sodium or potassium acetate was used during polymerization to minimize the degree of DEG formation and incorporation into the polymer.

Article Formation Film samples are an indication of improved barrier properties obtained from the present invention. The nanocomposite is prepared by in situ polymerization of the base polymer in the presence of sepiolite-type clay as described above. Nanocomposites can be used to make films, sheets or containers by any method known to those skilled in the art. Films, sheets and containers comprising nanocomposites exhibit increased tear strength, increased tensile modulus, reduced permeability for water vapor, oxygen and carbon dioxide, retaining high levels of toughness and transparency .

  Polyester nanocomposites can be used alone or as a component of a polymer blend. Although not limited thereto, additives commonly used in the industry such as antioxidants, antistatic agents, heat stabilizers, UV stabilizers, lubricants and antiblocking agents can be incorporated.

  Articles of the present invention include, but are not limited to, films, sheets, containers, membranes, laminates, pellets, coatings or foam forms or comprise thereof. Articles may be made by any means known in the industry including, but not limited to, injection molding, (co) extrusion, blow molding, thermoforming, solution casting, lamination and film blowing. In a particularly preferred embodiment, the article is an injection stretch blow molded bottle.

  Preferred articles of the present invention include food, personal care (health and hygiene) items and cosmetic packages. “Packaging” means either the entire package or a component of the package. Packaging components include, but are not limited to, packaging films, liners, shrink bags, shrink wraps, trays, tray / container assemblies, replaceable and non-replaceable caps, lids and beverage bottlenecks Is exemplified.

  The package may be in any form suitable for a particular application, such as a can, box, bottle, jar, bag, cosmetic package or end closure tube. Packaging may be constructed by any means known in the art such as, but not limited to, extrusion, coextrusion, thermoforming, injection molding, lamination or blow molding.

  Some specific examples of personal care and cosmetic packaging include, but are not limited to, food and non-prescription and prescription capsules and pills, solutions, creams, lotions, powders and shampoos. , Bottles, jars and caps for suspensions and lip products in contact with hair, conditioners, deodorants, antiperspirants, eyes, ears, nose, throat, nitrogen, urethra, rectum, skin, hair.

Examples The invention is further defined by the following examples. These examples illustrate preferred embodiments of the present invention, but are considered to be illustrative only. From the above description and these examples, those skilled in the art will be able to ascertain essential features of the invention without departing from the spirit and scope thereof, and various aspects of the invention may be adapted to various uses and conditions. Changes and modifications can be made.

The meanings of the abbreviations are as follows. “Min” is minutes, “m” is meters, “cm” is centimeters, “mm” is millimeters, “μm” is micrometers, “kg” is kilograms, “g” is grams, “lb” is pounds, “M” is mole, “MPa” is megapascal, “wt%” is weight percent (percentage), “DMT” is dimethyl terephthalate, “NMR” is nuclear magnetic resonance, “SEC” is size exclusion chromatography, “M “ _n ” is number average molecular weight, “RPM” is revolutions per minute, “psi” is pounds per square inch, “ksi” is kilo pounds per square inch, “MD” is machine direction, “TD” is cross direction, And “ND” is not determined.

Materials Dimethyl terephthalate (CAS # 120-61-6, 99%) was purchased from INVISTA (Wichita, Kansas). Ethylene glycol (CAS # 107-21-1) was purchased from Universa USA (Kirkland, Washington). Antimony oxide (CAS 1309-64-4, 99%) and manganese acetate (CAS # 6156-78-1, 99%) purchased from Aldrich Chemical Company (Milwaukee, Wisconsin) did. PANGEL® B20 sepiolite was purchased from EM Sullivan Associates. The control PET sample used was CRYSTAR (R) 3934 (E.I. du Pont de Nemours & Co., Wilmington, DE). Inc., Wilmington, Del.) Two EASTAR® PETG grades were purchased from Eastman Chemical Company (Kingsport, Tennessee).

Analytical Method The size exclusion chromatography system is a model alliance (Waters Corporation, Milford, Mass.) Equipped with a Waters 410® refractive index detector (DRI) (Milford, Mass.). Consists of Model Alliance 2690® and model number T-60A® dual detector module of Viscotek Corporation (Houston, TX) incorporating static right angle light diffusion A differential capillary viscometer detector was used for molecular weight determination. The mobile phase was 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) in 0.01 M sodium trifluoroacetate. The dn / dc for the polymer was measured and assumed that all samples were completely eluted during the measurement. The percentage of diethylene glycol (DEG) was determined using ¹ H NMR spectroscopy.

  The tensile properties of the nanocomposite film were determined according to ASTM procedure D882. MOCON® PERMATRAN-W® (MOCON®, Minneapolis, Minnesota) at 25 ° C. and 100% relative humidity According to ASTM procedure D6701, the water vapor transmission rate was examined. The degree of yellowness was evaluated visually or as described above according to ASTM D1003 at 50% relative humidity.

Example 1
Polyester / Sepiolite Nanocomposite Preparation Into a stainless steel autoclave, DMT (10.1 lb, 4.59 kg), ethylene glycol (6.7 lb, 3.0 kg), antimony trioxide (2.80 g), manganese acetate (3.60 g) ), Sodium acetate (1.30 g) and PANGEL® B20 sepiolite (140.0 g). The reaction vessel was purged three times with 60 psi nitrogen. The container was heated to 240 ° C. with a low flow nitrogen sweep of the container. The reaction was stirred at 25 RPM while the vessel was heated to 240 ° C. The reaction temperature was maintained for 10 minutes after the vessel reached 240 ° C. The reaction was heated to 275 ° C. and a 90 minute vacuum reduction cycle was initiated. Upon completion of the vacuum reduction cycle, a full vacuum (0.1 torr) was applied to the reaction and the reaction was maintained at 275 ° C. for 120 minutes. The reaction was pressurized with nitrogen and the polymer was extruded as a strand, cooled in a water tank and chopped into pellet form. The polymer molecular weight was determined using SEC. Mn = 24600,% DEG = 2.89%. This material is hereinafter referred to as “PET-Example 1”.

Example 2
Preparation and Properties of Films Containing 3% by Weight Sepiolite CRYSTAR® polyester polymer (unfilled) as a reference and polyester / sepiolite nanocomposite prepared in Example 1 (3% by weight sepiolite) Dried overnight at 120 ° C. under vacuum. The 30 mm twin screw extruder was equipped with a 10 inch (25.4 cm) film die and a feeder with a nitrogen blanket. The barrel was heated to a temperature of 255 ° C and the die was heated to 265 ° C. The film was extruded and cooled on a cooling casting drum. No filter screen was used during extrusion. Transparency and color were evaluated visually. Tensile modulus and WVTR were measured as described above. The results are shown in Table 1.

Example 3
Preparation of PET and copolyester sheets containing sepiolite Control CRYSTAR® polyester polymer (unfilled) and the polyester / sepiolite nanocomposite prepared in Example 1 (3 wt% sepiolite) Polyester Easter (R) 21446 and Easter (R) 6763 were dried at 120 [deg.] C. under vacuum overnight. The 30 mm twin screw extruder was equipped with a 10 inch (25.4 cm) film die and a feeder with a nitrogen blanket. The barrel was heated to a temperature of 255 ° C and the die was heated to 265 ° C. Samples 3A, 3B, 3C and 3D feeds are the PET nanocomposite composition of Example 1 ("PET-Example 1"), the weight of PET-Example 1 and EASTAR 21446. 1: 1 pellet blend on a basis, PET—Example 1 and EASTAR® 6763 by weight 1: 1 pellet blend and CRYSTAR® 3934 control. A 35 mil (889 μm) thick sheet was extruded and cooled on a cooling casting drum. No filter screen was used during extrusion. The degree of yellow was measured according to ASTM D1003. It shows in Table 2. The tensile properties are shown in Table 3.

Claims (13)

Method for reducing gas permeability of a molded thermoplastic polymer article formed from at least one polymer or polymer blend selected from polyester homopolymers, polyester copolymers and polymer blends comprising at least one such homopolymer or copolymer Because
(A) an amount of exfoliated sepiolite-type clay effective to reduce gas permeability,
(I) at least one diacid or diester and at least one diol,
(Ii) at least one polymerizable polyester monomer,
Preparing a nanocomposite by mixing with (iii) at least one linear polyester oligomer, and (iv) at least one polyester precursor selected from at least one macrocyclic polyester oligomer;
(B) polymerizing at least one polyester precursor;
(C) viewing including forming a molded article,
The at least one diacid or diester is terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, fumaric acid, maleic acid And a dialkyl ester thereof,
The at least one diol is ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 2,2-diethyl-1,3-propanediol, or 2,2-dimethyl-1,3-propanediol. 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2, 2,4,4-tetramethyl-1,3-cyclobutanediol, isosorbide, naphthalene glycol, diethyl Glycol is selected triethylene glycol, resorcinol, hydroquinone, and from the group consisting of long chain diols and polyols which are the reaction products of alkylene oxides with a diol or polyol,
The at least one polymerizable polyester monomer is a hydroxy acid, lactide,
Bis (2-hydroxyethyl) terephthalate, bis (4-hydroxybutyl) terephthalate, bis (2-hydroxyethyl) naphthalenedioate, bis (2-hydroxyethyl) isophthalate, bis [2- (2-hydroxyethoxy) ethyl Terephthalate, bis [2- (2-hydroxyethoxy) ethyl] isophthalate, bis [(4-hydroxymethylcyclohexyl) methyl] terephthalate, bis [(4-hydroxymethylcyclohexyl) methyl] isophthalate and mono (2-hydroxy) Selected from the group consisting of ethyl) terephthalate,
The at least one macrocyclic polyester oligomer is 1,4-butylene terephthalate, 1,3-propylene terephthalate, 1,4-cyclohexylenedimethylene terephthalate, ethylene terephthalate, 1,2-ethylene 2,6-naphthalene. A cyclic ester dimer of carboxylate, terephthalic acid and diethylene glycol, or a macrocyclic polyester oligomer of two or more macrocyclic co-oligoesters,
A method characterized by that .   The method of claim 1, wherein the polyester precursor is polymerized in the presence of a solvent.   The process according to claim 1, wherein the polymerization is carried out in the presence of 100 to 600 ppm of lithium acetate, sodium or potassium. Polyester homopolymers or copolymers are poly (ethylene terephthalate), poly (1,3-propylene terephthalate), poly (1,4-butylene terephthalate), poly (1,4-butylene terephthalate) and poly (tetramethylene ether) glycol blocks The process of claim 1 selected from thermoplastic elastomeric polyesters having the following: poly (1,4-cyclohexyldimethylene terephthalate), polylactic acid , and two or more copolymers thereof. Polymer is 2 mole percent to 5 bottle grade modified with isophthalate units up mole% poly (ethylene terephthalate), exfoliated sepiolite-type clay is, the weight of the modified polyethylene terephthalate used as a reference 0. The process according to claim 1, wherein the process is present at a concentration of from 01% to 6.0% by weight.   The method of claim 1 wherein the forming is selected from (co) extrusion, injection molding, blow molding, injection stretch blow molding, extrusion blow molding, lamination, thermoforming and film blowing.   Molded article is film, sheet, container, membrane, laminate, pellet, coating, foam, package or packaging member, bottle, box, jar, can, bag, end closure tube, cosmetic package, liner, lid, replaceable or 2. The method of claim 1 selected from disposable container caps, films, shrink wrap materials, shrink bags, trays, tray / container assemblies and beverage bottlenecks. A molded article comprising exfoliated sepiolite-type clay nanocomposites in a polyester homopolymer, polyester copolymer or polymer blend comprising at least one such homopolymer or copolymer comprising :
(I) at least one diacid or diester and at least one diol,
(Ii) at least one polymerizable polyester monomer,
(Iii) at least one linear polyester oligomer, and
(Iv) at least one macrocyclic polyester oligomer
The nanocomposite is prepared from at least one polyester precursor selected from:
The at least one diacid or diester is terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, fumaric acid, maleic acid And a dialkyl ester thereof,
The at least one diol is ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 2,2-diethyl-1,3-propanediol, or 2,2-dimethyl-1,3-propanediol. 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2, 2,4,4-tetramethyl-1,3-cyclobutanediol, isosorbide, naphthalene glycol, diethyl Glycol is selected triethylene glycol, resorcinol, hydroquinone, and from the group consisting of long chain diols and polyols which are the reaction products of alkylene oxides with a diol or polyol,
The at least one polymerizable polyester monomer includes hydroxy acid, lactide, bis (2-hydroxyethyl) terephthalate, bis (4-hydroxybutyl) terephthalate, bis (2-hydroxyethyl) naphthalenedioate, bis (2- Hydroxyethyl) isophthalate, bis [2- (2-hydroxyethoxy) ethyl] terephthalate, bis [2- (2-hydroxyethoxy) ethyl] isophthalate, bis [(4-hydroxymethylcyclohexyl) methyl] terephthalate, bis [ Selected from the group consisting of (4-hydroxymethylcyclohexyl) methyl] isophthalate and mono (2-hydroxyethyl) terephthalate;
The at least one macrocyclic polyester oligomer is 1,4-butylene terephthalate, 1,3-propylene terephthalate, 1,4-cyclohexylenedimethylene terephthalate, ethylene terephthalate, 1,2-ethylene 2,6-naphthalene. A cyclic ester dimer of carboxylate, terephthalic acid and diethylene glycol, or a macrocyclic polyester oligomer of two or more macrocyclic co-oligoesters,
A molded article characterized by that . Film, sheet, container, membrane, laminate, pellet, coating, foam, package or packaging member , bottle, box, jar, can, bag, end closure tube, cosmetic package, liner, lid, replaceable or disposable container cap 9. Molded article according to claim 8, selected from : film, shrink wrapping material, shrink bag, tray, tray / container assembly or beverage bottleneck. Is formed by stretch blow molding out morphism, and formed from a polyester nanocomposite, polyester is polyethylene terephthalate bottle grade modified with isophthalate units up to 2 mole% to 5 mole%, of exfoliated sepiolite-type clay, molded article according to claim 8, the weight of the modified polyethylene terephthalate used as the reference is present in a concentration from 0.1 wt% to 6.0 wt%. a. At least one polyester; and b. A nanocomposite composition comprising exfoliated sepiolite-type clay ,
The at least one polyester is
(I) at least one diacid or diester and at least one diol,
(Ii) at least one polymerizable polyester monomer,
(Iii) at least one linear polyester oligomer, and
(Iv) at least one macrocyclic polyester oligomer
Prepared from at least one polyester precursor selected from
The at least one diacid or diester is terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, fumaric acid, maleic acid And a dialkyl ester thereof,
The at least one diol is ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 2,2-diethyl-1,3-propanediol, or 2,2-dimethyl-1,3-propanediol. 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2, 2,4,4-tetramethyl-1,3-cyclobutanediol, isosorbide, naphthalene glycol, diethyl Glycol is selected triethylene glycol, resorcinol, hydroquinone, and from the group consisting of long chain diols and polyols which are the reaction products of alkylene oxides with a diol or polyol,
The at least one polymerizable polyester monomer includes hydroxy acid, lactide, bis (2-hydroxyethyl) terephthalate, bis (4-hydroxybutyl) terephthalate, bis (2-hydroxyethyl) naphthalenedioate, bis (2- Hydroxyethyl) isophthalate, bis [2- (2-hydroxyethoxy) ethyl] terephthalate, bis [2- (2-hydroxyethoxy) ethyl] isophthalate, bis [(4-hydroxymethylcyclohexyl) methyl] terephthalate, bis [ Selected from the group consisting of (4-hydroxymethylcyclohexyl) methyl] isophthalate and mono (2-hydroxyethyl) terephthalate;
The at least one macrocyclic polyester oligomer is 1,4-butylene terephthalate, 1,3-propylene terephthalate, 1,4-cyclohexylenedimethylene terephthalate, ethylene terephthalate, 1,2-ethylene 2,6-naphthalene. A cyclic ester dimer of carboxylate, terephthalic acid and diethylene glycol, or a macrocyclic polyester oligomer of two or more macrocyclic co-oligoesters,
A nanocomposite composition characterized by the above . Exfoliated sepiolite-type clay A composition according to claim 11 which is present at a concentration of exfoliated and sepiolite-type based on the weight of polyester plus clay of 0.1% to 2 0% by weight.   The composition according to claim 11, wherein the polyester is poly (ethylene terephthalate), poly (1,3-propylene terephthalate), poly (1,4-butylene terephthalate) or poly (1,4-cyclohexyldimethylene terephthalate). object.